Вы находитесь на странице: 1из 16

JKAU: Eng. Sci., vol. 15 no. 1, pp. 3-17 (1425 A.H./ 2004 A.D.

Production Of Liquid Alum Coagulant From


Local Saudi Clays
A. AL-ZAHRANI & M. H. ABDEL-MAJID
Chemical & Materials Engineering Dept., King Abdul-Aziz University
P.O. Box 80204, Jeddah 21589
ABSTRACT. This study was carried out to investigate the use of
local clays extremely abundant in the Kingdom for production of
liquid alum. Local kaolinitic clay containing 29.4% Al2O3 was
ground, activated by calcination and treated with sulfuric acid
solution to extract alumina. In the activation step, the effects of
grain size of clay, temperature and period of calcination on the
extraction of alumina and iron oxide are investigated. Leaching
experiments were conducted using the stoichiometric requirement
of 40 wt. % H2SO4 for one hour under boiling conditions. Clay
samples of particle size ranging from 8 to 200 mesh standard
Tyler screens, calcined at different temperatures ranging from 450
to 1000 oC and for different periods ranging from 15 to 180
minutes were used. The results revealed that 90.9% of Al2O3 can
be extracted when using 65 mesh clay, calcined at 700 oC for one
hour. Experiments on the effect of acid concentration on alumina
extraction from clay under the above conditions indicate that 40
wt.% acid is the recommended as it gives high extraction of
alumina and at the same time results in free flowing properties of
the reaction mixture. Leaching experiments were performed to
investigate the effects of acid to clay ratio (50 to 120%) and
leaching period (0.25 to 3 hrs) on alumina extraction. The results
indicate that 88.6% of Al2O3 could be extracted when using 88.1%
of stoichiometric requirement of 40 wt.% acid for two hours
leaching period under boiling conditions.

1. Introduction
Liquid Alum is a solution of aluminum sulfate having the general chemical
formula Al2(SO4)3.xH2O. For many years, 17% alum in solid form was easy to

A. Al-Zahrani and M. H. Abdel-Majid

package and economical to ship over long distances. However, liquid alum has
become more popular now because of its lower cost in handling and storage.
Several processes have been suggested for producing aluminum sulfate
from clay. Most of the reported processes include calcination of clay before
extracting alumina by treatment with sulfuric acid. In most reported literature,
the effect of clay grinding before calcination was not paid enough attention.
Some of the reported literature recommended calcination temperature of 790oC
[1] or 770- 820oC [2]. Others [3] reported a recommended temperature of 550oC
and mentioned that if kaolin is not heated, the solubility vanishes. It was
reported [4] that kaolin is not markedly affected by previous ignition of the
sample, but ignition of the mineral pyrophyelite (Al2O3. 4 SiO2.H2O) causes a
marked increase in alumina extraction. It was also reported that heating at 700
800oC for one hour could be practiced if alumina is extracted from highly
aluminous clays [5]. When sulfuric acid was added to kaolin prior to heating,
the calcination temperature was about 850oC [6]. Pressure was applied after
heating kaolin to 600oC to extract aluminum oxide [7].
Different concentrations of sulfuric acid were reported for extraction of
alumina from calcined clays. It was reported that, in general, the extraction of
alumina from calcined clays increases with increasing duration of extraction at a
fixed temperature and also increases by increasing temperature at a fixed
duration of extraction. Concentration of about 70 wt.% H2SO4 has been
patented to produce aluminum sulfate [8]. When kaolin was heated to 1100
1200oC for one hour, then boiling calcined kaolin with sulfuric acid of
concentration 5 7 wt.% H2SO4 for one hour, alumina extraction was about
80% [9]. Leaching with sulfuric acid was practiced at 90oC and 10 20 % acid
concentration [10]. Another patent reported 30 wt. % acid concentration as the
recommended concentration [11]. A temperature of 105oC has been reported [8]
as a recommended extraction temperature. Another patent recommended a
temperature of 70 90oC for 10 12 hours to extract 70 80 % of alumina
[12].
Other articles were reported for the production of aluminum sulfate for
different types of clays [13-20], from aluminum industry wastes [21-24] or from
different industrial wastes [25-29]. The use of amines for extracting iron from
aluminum sulfate leach liquor was also reported [30-31].]
In this paper, the possibility of manufacturing liquid alum from Saudi
clays to satisfy local demands of coagulant aluminum sulfate which are
extremely abundant in the Kingdom will be investigated. A bench scale study
was carried out to investigate the activation of Saudi clay by calcination method
and the leaching of alumina from the calcined clay by treatment with sulfuric

Production Of Liquid Alum Coagulant From Local Saudi Clays

acid. The effect of different variables on both activation and leaching steps is
investigated to recommend the most effective conditions for both processes.
2. Materials And Methods
2.1 Materials
The clay samples used in this study is native kaolinitic clay obtained
from Az-Zabirah area. Chemical analysis of the ground clay sample was carried
out according to the standard methods [32,33]. The analysis is given in Table 1.
The sulfuric acid used was BDH general purpose reagent.
Table 1. Chemical Composition of Local Kaolinitic Clay
Compound
SiO2

Natural local clay (wt.%)


47.25

Al2O3

29.4

Fe2 O3

2.87

TiO2
MgO
CaO
K2O

1.17

Na2O

2.11

MnO
SO3

< 0.05
< 0.05

P2O5
L.O.I.

< 0.05

0.35
0.59
0.17

16.02

2.2 Experimental
The equivalent diameter of the raw local clay sample was about 2 to 3
inches. The clay sample was ground using a ball mill to pass a sieve of a
specified mesh number ranging from 8 to 200 mesh (standard Tyler screens).
For each standard sieve, the ground clay sample was placed on the sieve, and
then mechanically shaked for 5 minutes. The oversize was further ground
followed by sieving on the same sieve. The procedures were repeated till the
entire clay sample passed through the sieve.
Twenty five grams of the ground clay sample were subjected to
calcination. A muffle furnace with a maximum temperature of 1200oC was

A. Al-Zahrani and M. H. Abdel-Majid

used. The heating covered a range of temperature between 450oC to 1000oC


with a heating interval of 50oC. The duration of calcination was varied from 15
minutes to 180 minutes.
The calcined kaolin samples were extracted by sulfuric acid of certain
concentration. A range of acid concentration from 20 to 40% by weight was
studied. This range was chosen to fulfill a relatively high acid concentration and
at the same time to keep the fluidity of the resulting mixture. Leaching tests
were then followed using 40% weight sulfuric acid leachant to investigate the
effect of the following variables on the extraction step:
i- Reaction time: the effect of reaction time was studied over a range from
15 minutes to 3 hours at boiling conditions.
ii- Acid to clay ratio: the effect of acid to clay ratio was studied over a range
from 50% to 120%. The acid to clay ratio equals the quantity of acid used
divided by the stoichiometric quantity of acid required.
By the end of extraction, the resulting slurry was filtered then washed. The
filtrate and washings are completed to a constant volume then diluted and
analyzed for aluminum and iron by inductively coupled plasma optical
emission spectrometer [34].
3. Results and Discussion
3.1 Effect of grain size
Figure 1 shows the effect of grain size of clay sample on the percentage
aluminum and iron oxides extraction. All samples were calcined at fixed
temperature of 700 oC for a fixed period of one hour. Then the calcined
samples were leached by sulfuric acid of 40 wt. % concentration using the
stoichiometric acid requirement for one hour at boiling conditions under total
reflux. The mesh number of the clay sample was varied over a wide range
between 8 and 200 standard Tyler screen mesh. Figure 1 indicates the
following points:
i- A relatively large increase in alumina extraction from 76.5 to 89.9% is
obtained when the grain size is varied from 8 to 35 mesh.
ii- A comparatively slight increase in the % extraction of alumina is
observed between the successive meshes 35 and 48 mesh.
iii- Nearly no significant change in the extraction of alumina is observed
between 48 and 200 mesh.
iv- The percent extraction of iron oxide between 8 and 35 mesh lies
between 40.8 and 47.8%. After 35 mesh, the effect of reducing the
size of the clay sample on percent extraction is negligible.

Production Of Liquid Alum Coagulant From Local Saudi Clays

100
90
80

Percent Extraction

70
60
50
40
30
20

Alumina
Iron oxieds

10
0
0

50

100

150

200

250

Mesh size (standard Tyler screen size)


Figure1. Effect of grain size on percent extraction. Calcination temp. 700 o C
for 1 hr. leaching with 40% by wt. H2SO4 at boiling conditions and a
grain size of mesh no. 65 (standard Tyler screen mesh).

These results indicate that grinding the clay samples beyond 48 mesh has
no significant effect on the extraction of alumina from local clay sample. This
indicates that the grain size of -48 to-52 mesh is quite suitable for grain size to
be used. This will also benefit in reducing excessive grinding cost. A grain size
of 65 mesh was selected for further work.
3.2 Effect of Temperature and Time of Calcination
The effect of varying duration and temperature of calcination on the
percent extraction of alumina and iron oxide is indicated in Tables 2 and 3 and
Fig. 2. The data indicate the following points:

A. Al-Zahrani and M. H. Abdel-Majid

Production Of Liquid Alum Coagulant From Local Saudi Clays

100
90
80

Percent Extraction

70
60
50
40
30

Al2O 3
Fe2O 3

20
10
0
500

600

700

800

900

1000

Temperature C

Figure 2. Effect of calcination temperature on percent extraction Calcination


time of hr, leaching with 40% by wt. H2SO4 at boiling conditions
and a grain size of mesh no. 65 (standard Tyler screen mesh).

i.
ii.
iii.

An inert zone below 450 oC, during which the percent extraction of
alumina is small.
A promising zone from 500 oC to 750 oC during which percent
extraction of alumina increases. The percent extraction decreases
sharply when the temperature exceeds 800 oC.
The highest alumina extraction (91.1%) is reached at a calcination
temperature of 750 oC and for a duration time of one hour as can be
seen from Table (1). However the increase in percentage of alumina
extraction when temperature increases from 700 to 750 oC is only 0.2
%. This slight increase does not justify the corresponding increase in
energy requirement. Therefore, a temperature of 700 oC is
recommended for further experimental work.

A. Al-Zahrani and M. H. Abdel-Majid

10

3.3 Effect of Acid Concentration


The effect of acid concentration on the extraction of alumina is shown in
Fig. 3, for 65 mesh clay calcined at 700 oC for one hour and extracted with the
stoichiometric amount of sulfuric acid under boiling conditions. The alumina
extraction increases moderately as the acid concentration increases. An acid
concentration of 20% by weight corresponds to 88.6 % extraction while 40%
concentration results in 90.9 % extraction and 60% concentration corresponds
to 92.9 % extraction. The corresponding values for iron oxide extraction are
50.3, 48.0 and 55.7 %, respectively.
The difference in % alumina extraction between 40% and 60% acid
concentration is not large. However at 60% acid concentration, the reaction
mixture became pasty. During the course of the study of the time of the
reaction, it was noted that when using 40% acid concentration and an acid to
clay ratios below 100%, the reaction mixture was just free flowing. This makes
it undesirable to increase the acid concentration beyond the 40% concentration.
100

90

Percent Extraction

80

70

60

50
Al2O3

40

30
10

Fe2O3

20

30

40

Concentration of H2SO4
( %)

50

60

70

Figure 3. Effect of acid concentration on extraction of Al2O3 & Fe2O3.


Grain size: -65 mesh standard Tyler screen and calcination temperature at
700 o C for 1 hr.

Production Of Liquid Alum Coagulant From Local Saudi Clays

11

3.4 Effect of Time of Extraction


The effect of extraction time on the yield of alumina extracted from 65
mesh clay calcined at 700 oC for one hour using 40 wt.% sulfuric acid under
boiling conditions and different acid to clay ratios is shown in Figure (4). The
figure shows that for an acid to clay ratio greater than 80%, the percent
extraction of alumina from the clay is almost constant after two hours.
Therefore, a reaction time of two hours is recommended. The corresponding
results for iron oxide are shown in Figure (5)
60

Percent Fe2O3 Extraction

50

40

30

50%

20

60%
70%
80%
90%
100%

10

110%
120%

0
0

Time of extraction (hr)

Figure 4. Effect of extraction time on % Fe2O3 extraction at different acid to clay ratios.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C.

3.5 Effect of Acid to Clay Ratio


The results of the effect of cid to clay ratio on 65 mesh clay calcined to
700 oC for one hour and extracted at the boiling conditions for one hour by
using 40% concentrated acid are given in Figure (6). The data shows a large
increase in the percentage extraction of aluminum oxide from 63.6% when half
the stoichiometric quantity of the acid is used to 91.8% when 120% of the
stoichiometric quantity is used. Corresponding values for extraction of iron
oxide are 23.3% and 48.8%, respectively as shown in Figure (7).

A. Al-Zahrani and M. H. Abdel-Majid

12

60

50

Percent Fe2O3 Extraction

40

30

50%

20

60%
70%
80%

10

90%
100%
110%
120%

0
0

Time of extraction (hr)

Figure 5. Effect of extraction time on % Fe2O3 extraction at different acid to clay ratios.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C for 1 hr
and leaching with 40% by wt. H2SO4 at boiling conditions.

Figure (8) shows a comparison between the theoretical and actual percent
extractions for Al2O3 and Fe2O3. Acid to clay ratio above 120% does not appear
to give any sign of increase in the yield of alumina. The point of intersection
between the straight line, representing the theoretical conditions and the
experimental curve, corresponds to 88.1% acid to clay ratio and 88.6% alumina
extraction, which means complete reaction of the acid added with alumina in
the clay. Acid to clay ratio above 88.1% results in the presence of free unreacted
acid. Acid to clay ratio below 88.1% shows higher values than those expected
theoretically which indicates that such solutions of extracted aluminum sulfate
contain dissolved alumina. Analysis of the liquor obtained after filtration gives
17% Al2O3 content whereas analysis of combined filtrate and washing gives
8.1% Al2O3, which is within the commercial requirements for liquid alum to
avoid crystallization of aluminum sulfate and therefore no concentration step
needed.

Production Of Liquid Alum Coagulant From Local Saudi Clays

13

10

Percent Al2O3 Extraction

90

80

70

1/14 hr

60

1/2 hr
1 hr
2 hrs
3 hrs

50

40
30

50
70
90
110
Acid: clay ratio (% of stoichiometric)

130

Figure 6. Effect of acid to clay ratio on extraction of Al2O3 at different leaching periods.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C for 1 hr
and leaching with 40% by wt. H2SO4 at boiling conditions.

3.6 Effect of Temperature of Extraction


The study of the optimum conditions of the temperature of extraction is
limited by the need for conducting the extraction under boiling conditions to
hydrolyze and therefore precipitates any dissolved titanium salts. Extraction of
alumina from calcined clay at temperature below the boiling temperature results
in rendering titanium impurities present in the clay soluble in solution.
However, at the boiling conditions, soluble titanium sulfate is hydrolyzed to
insoluble form and therefore prevent contamination with the product.
4. CONCLUSIONS
The optimum conditions for production of aluminum sulfate for Saudi clay
are: grinding the clay to pass 65 mesh sieve (standard Tyler screens),
calcination of the ground clay at 700 oC for one hour, extraction of alumina
from calcined clay by leaching with 40% by weight sulfuric acid, using 88.1%
of stoichiometric acid to clay ratio and extraction at boiling conditions for two
hours

A. Al-Zahrani and M. H. Abdel-Majid

14
50

Percent Fe2O3 Extraction

40

30

20

1/14 hr
1/2 hr
1 hr
t2 hrs
3 hrs

10
20

40
60
80
100
12
Acid: clay ratio (% of stoichiometric)

140

Figure 7. Effect of acid to clay ratio on extraction of Fe2O3 at different leaching periods.
Grain size: -65 mesh standard Tyler screens, calcination at 700 o C for 1 hr
and leaching with 40% by wt. H2SO4 at boiling conditions.
100
90
80

Percent Extraction

70

60
50
40
30
20
Al2O3
Fe2O3
Theo

10
0
30

50

70

90

110

130

Acid: clay ratio (% of stoichiometric)

Figure 8. Effect of acid to clay ratio on extraction of Al2O3 & Fe2O3 .


Grain size: -65 mesh standard Tyler screens, calcination at 700 o C for 1 hr
and leaching with 40% by wt. H2SO4 at boiling conditions.

Production Of Liquid Alum Coagulant From Local Saudi Clays

15

Leaching the Saudi clay at the above conditions will result in 89.5 %
extraction of the alumina content in the clay. The product liquid alum contains
8.1% Al2O3 which corresponds to about 23.4% Al2(SO4)3.
Acknowledgement: This work was supported by Scientific Research Council,
King AbdulAziz University (Jeddah, Saudi Arabia) under grant number
119/422.
REFERENCES
[1
[2]
[3
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]

Hertz, J. G., Aluminum Sulphate from Rumanian Clays, Rev. Chim. (Bucharest) 5, 513- 18,
1954.
Stein, J. G., Production of Alumina from Clay or Other Aluminous Ore, Brit, Pat. No. 480,
921, March 1938.
Bagbany, I. L. and Zeinalove, Kh. L., Preparation of Aluminum Sulphate from Kaolin
Clays , Trudy Inst. Khim., Akad, Nauk, Azeraidzhan S. S. R., 13, 104-12, 1954.
Sutton, R. A., Extraction of Alumina from Clays by Sulphuric Acid , Records Geol. Survey
Tanganyika , 1, 59, 1951.
Abdul Kaseem, Shabir Qureshi, Iqbal Ahmad and Karim Ullah., Extraction of Alumina
from High-Aluminous Clays , Pakistan J. Sci. Research, 8, 88-93, 1956.
Minerals and Chemicals Corp. of America, Clay Activation by Acid Treatment and
Calcination , Brit. Pat. No. 793, 393, April 1958.
Dybina, P. V., Sulphite Decomposition of Kaolin , Klim. Prom., No. 3, 8-11, 1953.
Hyslop, J. F., Obtaining Alumina from Clay , Brit., Pat. No. 480, 921, March 1937.
Fialkov, Ya. A. and Shargorodski, S. D., Obtaining Aluminum Oxide from the Product of
Sintering Sodium Sulphate with Kaolin, Zapiski Inst. Khem., Ukrain, Akad, Nauk, 5, 487505, 1938.
Sharp, F. H., Process for producing Aluminum , U.S. Patent, No. 2,487,076, Nov.
1949.
Haff, R. C., Method of Recovering Alumina from Alumina Bearing Ores , U.S. Patent No.
2. 555, 944, May 1951.
Stanislaw Bretsznajder, Obtaining Pure Aluminum Compounds from Clays and Kaolins,
Tech. Univ. Warsaw Zeszyty Nauk, Pilotech, Warzaw, No. 9, Chm. No. 1, 1159, 1954.
Hertz, A., Aluminum Sulphate from Rumanian Clay , REV. Chem., Bucharest, V. 5, 513518,
1951.
Mitwally, H., Production of Aluminum Sulphate from Egyptian Kaolin for use as
Coagulant in Water Treatment , Ph.D. Thesis, Alexandria University, Egypt, 1962.
Aly, F., El-Shawarby, S., Eissa, S., and Chlabi, M., Production of Aluminum Sulphate
from Aluminum Oxide from Egyptian clays- 2. Dissolution Kinetic of Aluminum Oxide
from Egyptian Clays in Sulphuric Acid , J. Mines-Metals-Fuels, V. 29, 360-366, 1981.
Schulize, E., Eisele, J., Morimoto, M., and Bauer, D., Extracting Iron from Aluminum
Sulphate Leach Solution , U.S. Bureau of Mines Rept. Of Inv. 8353, 1-19, 1979.
Chou, K.J. and Chuen, C.L., Extracting Iron from Aluminum Sulfate Solution,
Hydrometallurgy, 3, 391-397, 1986.
Fernandez, A., Ibanez, J., Liavana, M., and Zapico, R., Leaching of Aluminum in Spanish
Clays, Coal Mining Wasted and Coal Fly Ashes by Sulphuric Acid, Proc. of Minerals,
Metals & Materials Soc. (TMS), 121 130, Warren dale, Pennsylvania, U.S.A., 1998.
Peters, A. and Johnson, P., Methods of Producing Alumina from Clay An Evaluation of
Two Ammonium Alum Processes , U.S. Bureau of Mines Report of Inv., 6573, 1965.
Peters, A., Johnson, P., and Kirby, R., Methods of Producing Alumina from Clay An

16

[21]
[22]
[23]
[24]
[25]

[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]

A. Al-Zahrani and M. H. Abdel-Majid

evaluation of Three Sulfuric Acid Processes , U.S. Bureau of Mines Report of Inv., 6229,
1962.
Peters, A., Johnson, P. and Kirby, R., Methods of Producing Alumina from Clay An
evaluation of Three Sulfuric Acid- Caustic Purification Process, U.S. Bureau of Mines
Report of Inv., 5997, 1962.
Park, S.S, Hwang, E.H., Kim, B.C. and Park, H.C., Synthesis of Hydrated Aluminum
Sulfate from Kaolin by Microwave Extraction , Journal of American Ceramic Society, 83,
1341 1345, 2000.
Abd-Ezaher, M.M. and Hamzawy, E.M.A, Extraction of Alumina from Aluminum Slag
Using Different Salts , Journal for Exploration, Mining and Metallurgy, 54, No. 4, 208
213, 2001.
Saunders, F.M. and Harmon, C.B.,
Production of Liquid Alum from AluminumAnodizing Sludges , Water Science and Technology, 17, No. 4 5, 541 550, 1985.
Osborne, B.W., Use of Primary Dross from the Aluminum Industry for Manufacturing
Aluminum Sulfate , 3rd International Symposium on Recycling of Metals and Engineered
Materials Proceedings on the TMS Fall Meeting 1995. Minerals, Metals & Materials Soc
(TMS), Warrendale, PA, USA, 947 954, 1995.
Mohamed, M. A., Kassim, M.E. and El- Katatny, E.A., Optimization of Extraction of
Aluminum Sulfate and Ammonium Aluminum Sulfate Alums from Aluminum Dross
Tailing , Journal of Materials Research, V. 13, 4, 1075 1083, 1998.
Saunders, F.M., Innovative Treatment of Aluminum Anodizing Wastes for Recovery of
Aluminum , Aluminum Technology 86, Proceedings of International Conference, Institute
of Metals, London, England, 83 90, 1986.
Paunswad, T. and Chamnan, P., Aluminum Recovery from Industrial Aluminum Sludges,
Water Supply, V.10, 4, 159 166, 1992.
Bakr, M. Y., Mitwally, H.H. , Al-abd, M.A., El-Adawy, M.S., Abdel-Majid, M.H.,
Zatout, A.A. and Hamouda, A.A., Production of coagulants and coagulant Aids Locally,
Project Submitted for Academy of Scientific Research and Technology, Egypt, 1977.
Khalil, N.M.,
Refractory Aspects of Egyptian Alum-Waste Material Ceramics
International, V. 27, 6, 695 700, 2001.
Shimko, I. G, Chernetskii, E.K., Gens, A.M., and Biryukova, N.I., Regeneration of
Coagulant from Aluminum Hydroxide Containing Precipitates , Fibre Chemistry, v. 18, 326
328, 1986.
Vogel, A., A Text Book of Quantitative Inorganic Analysis 3 rd. ed., Longmans, UK, 1961.
Mondham, J., Denney, R., Barnes, J. and Thomas, M., Vogels, Text Book of Quantitative
Chemical Analysis , 6th. Ed., Prentice Hall, UK, 2000.
Operating Manual, Inductively Coupled Plasma Optical Emission Spectrometer, Optimal
4100 DV, Parkin Elmer, USA, 2000.

17

Production Of Liquid Alum Coagulant From Local Saudi Clays

- -
. .

:

.
%,
.



%



%,



%



%-
, . %.

A. Al-Zahrani and M. H. Abdel-Majid

%,
% .

18

Вам также может понравиться